Composition comprising a dibenzoylmethane screening agent and a merocyanine dicyano or cyanoacetate derivative; method for the photostabilization of the dibenzoylmethane screening agent

ABSTRACT

The present invention relates to a cosmetic composition comprising the combination i) of at least one screening agent of the dibenzoylmethane derivative type and ii) of at least one specific merocyanine dicyano or cyanoacetate derivative. It also relates to a method for the photostabilization, with regard to radiation, of at least one screening agent of the dibenzoylmethane derivative type by an effective amount of at least one specific merocyanine dicyano or cyanoacetate derivative.

This application is a Divisional of U.S. application Ser. No. 13/634,176filed on Nov. 27, 2012, which is the National Phase filing under 35U.S.C. §371 of PCT/EP2011/053378 filed on Mar. 7, 2011; and thisapplication claims priority to Application No. 1051819 filed in Franceon Mar. 15, 2010 under 35 U.S.C. §119, and this application claimspriority to Application No. 1058686 filed in France on Oct. 22, 2010under 35 U.S.C. §119; and this application claims the benefit of U.S.Provisional Application No. 61/282,735 filed on Mar. 24, 2010. Theentire contents of each application is hereby incorporated by reference.

The present invention relates to a cosmetic composition comprising thecombination i) of at least one screening agent of the dibenzoylmethanederivative type and ii) of at least one specific merocyanine dicyano orcyanoacetate derivative, the definition of which will be given below.

It also relates to a method for the photostabilization, with regard toradiation, of at least one screening agent of the dibenzoylmethanederivative type by an effective amount of at least one specificmerocyanine dicyano or cyanoacetate derivative, the definition of whichwill be given below.

It is known that light radiation with wavelengths of between 280 nm and400 nm makes possible browning of the human epidermis and that rays withwavelengths more particularly of between 280 and 320 nm, known under thename of UV-B, cause erythemas and skin burns which may be harmful to thedevelopment of natural tanning. For these reasons, and for aestheticreasons, there exists a constant demand for means for controlling thisnatural tanning for the purpose of thus controlling the colour of theskin; it is thus advisable to screen out this UV-B radiation.

It is also known that UV-A rays, with wavelengths of between 320 and 400nm, which cause browning of the skin, are capable of bringing about adetrimental change in the latter, in particular in the case of sensitiveskin or of skin continually exposed to solar radiation. UV-A rays causein particular a loss in the elasticity of the skin and the appearance ofwrinkles, resulting in premature skin ageing. They promote thetriggering of the erythemal reaction or accentuate this reaction in somesubjects and can even be the cause of phototoxic or photoallergicreactions. Thus, for aesthetic and cosmetic reasons, such as thepreservation of the natural elasticity of the skin, for example,increasingly people desire to control the effect of UV-A rays on theirskin. It is therefore desirable also to screen out UV-A radiation.

With the aim of providing protection of the skin and keratinoussubstances against UV radiation, use is generally made of antisuncompositions comprising organic screening agents which are active in theUV-A region and which are active in the UV-B region. The majority ofthese screening agents are fat-soluble.

In this respect, a particularly advantageous family of UV-A screeningagents is currently composed of dibenzoylmethane derivatives and inparticular 4-(tert-butyl)-4′-methoxydibenzoylmethane, this being becausethese exhibit a high intrinsic absorption power. These dibenzoylmethanederivatives, which are now products well known per se as screeningagents active in the UV-A region, are described in particular in FrenchPatent Applications FR-A-2326405 and FR-A-2440933, and in EuropeanPatent Application EP-A-0114607; furthermore,4-(tert-butyl)-4′-methoxydibenzoylmethane is currently provided for saleunder the trade name of “Parsol 1789 ®” by DSM Nutritional Products.

Unfortunately, it is found that dibenzoylmethane derivatives areproducts which are relatively sensitive to ultraviolet radiation (inparticular UV-A radiation), that is to say, more specifically, that theyexhibit an unfortunate tendency to decompose more or less rapidly underthe action of the latter. Thus, this substantial lack of photochemicalstability of dibenzoylmethane derivatives in the face of the ultravioletradiation to which they are by nature intended to be subjected does notmake it possible to guarantee continuous protection during prolongedexposure to the sun, so that repeated applications at regular and closeintervals of time have to be carried out by the user in order to obtaineffective protection of the skin against UV rays.

Patent Application WO 0128732 reveals a method for thephotostabilization of a dibenzoylmethane derivative by a merocyaninephenyl sulphone derivative. On the one hand, this photostabilization ofthe dibenzoylmethane derivative by the merocyanine phenyl sulphonederivative is not completely satisfactory. On the other hand, thesemerocyanine phenyl sulphone derivatives exhibit the disadvantage ofdecomposing in the presence of dibenzoylmethane under the influence ofUV radiation.

Provision has already been made, in Patent Application WO 2008090066, tophotostabilize dibenzoylmethane derivatives by cyclic derivatives ofmerocyanine cyanoacetate. Here again, the photostabilization of thedibenzoylmethane derivative remains inadequate and these merocyaninecyanoacetate derivatives also exhibit the disadvantage of decomposing inthe presence of dibenzoylmethane.

The photostabilization of dibenzoylmethane derivatives with regard to UVradiation thus constitutes a problem which to date has not been solvedin a completely satisfactory manner.

In point of fact, the Applicant Company has now just discovered,surprisingly, that, by combining the abovementioned dibenzoylmethanederivatives with at least one specific merocyanine dicyano orcyanoacetate derivative, the definition of which will be given below, itis possible to substantially further improve the photochemical stability(or photostability) of these same dibenzoylmethane derivatives and theireffectiveness in the UV-A region without the disadvantages indicatedabove.

This discovery forms the basis of the present invention.

Thus, in accordance with one of the subject-matters of the presentinvention, a composition is now provided comprising, in a cosmeticallyacceptable vehicle, at least one UV screening system, characterized inthat it comprises:

(i) at least one dibenzoylmethane derivative and(ii) at least one merocyanine dicyano or cyanoacetate derivative, thedefinitions of which will be given below.

Another subject-matter of the invention is also a method for improvingthe chemical stability with regard to UV radiation of at least onedibenzoylmethane derivative which consists in combining the saiddibenzoylmethane derivative with an effective amount of at least onemerocyanine dicyano or cyanoacetate derivative, the definitions of whichwill be given below.

Other characteristics, aspects and advantages of the invention willbecome apparent on reading the detailed description which will follow.

“Cosmetically acceptable” is understood to mean compatible with the skinand/or its superficial body growths, exhibiting a pleasant colour, apleasant odour and a pleasant feel, and not causing unacceptablediscomfort (smarting, tightness, redness) liable to dissuade theconsumer from using this composition.

“Effective amount” is understood to mean an amount sufficient to producea notable and significant improvement in the photostability of thedibenzoylmethane derivative or derivatives in the cosmetic composition.This minimum amount of merocyanine dicyano or cyanoacetate derivative asdescribed in detail later, which can vary according to the nature of thevehicle selected for the composition, can be determined without anydifficulty by means of a conventional test for measuring photostability,such as that given in the examples below.

Mention may in particular be made, among the dibenzoylmethanederivatives, without implied limitation, of:

-   2-methyldibenzoylmethane,-   4-methyldibenzoylmethane,-   4-isopropyldibenzoylmethane,-   4-(tert-butyl)dibenzoylmethane,-   2,4-dimethyldibenzoylmethane,-   2,5-dimethyldibenzoylmethane,-   4,4′-diisopropyldibenzoylmethane,-   4,4′-dimethoxydibenzoylmethane,-   4-(tert-butyl)-4′-methoxydibenzoylmethane,-   2-methyl-5-isopropyl-4′-methoxydibenzoylmethane,-   2-methyl-5-(tert-butyl)-4′-methoxydibenzoylmethane,-   2,4-dimethyl-4′-methoxydibenzoylmethane,-   2,6-dimethyl-4-(tert-butyl)-4′-methoxydibenzoylmethane.

Use will in particular be made, among the abovementioneddibenzoylmethane derivatives, of 4-isopropyldibenzoylmethane, sold underthe name of “Eusolex 8020” by Merck, which corresponds to the followingformula:

Preference is very particularly given to the use of4-(tert-butyl)-4′-methoxydibenzoylmethane or Butyl MethoxyDibenzoylmethane or avobenzone, provided for sale under the trade nameof “Parsol 1789” by DSM Nutritional Products Inc.; this screening agentcorresponds to the following formula:

The dibenzoylmethane derivative or derivatives can be present in thecompositions in accordance with the invention at contents whichpreferably vary from 0.01 to 20% by weight, more preferably from 0.1 to10% by weight and more preferably still from 0.1 to 6% by weight, withrespect to the total weight of the composition.

The merocyanine dicyano or cyanoacetate derivatives in accordance withthe present invention are chosen from the group consisting of:

(i) those corresponding to the following general formula (I):

in which:

-   -   A is the —C≡N or —(C═O)OR₃ group,    -   R₁ and R₂, which are identical or different, denote a linear or        branched C₁-C₃ alkyl radical, the hydroxyethyl group or a C₅-C₆        cycloalkyl,    -   R₃ denotes a linear or branched C₁-C₅ alkyl radical,    -   n is 1 or 2;        with the proviso that, when n=2, R₁, R₂ or R₃ is a C₂-C₁₆ alkyl        diradical or else R₁ and R₂ form, with 2 nitrogen atoms, a        cyclic divalent —(CH₂)_(m)— radical with m being an integer        ranging from 3 to 7;        (ii) the compound (a):

(iii) the compound (b):

(iv) the compound (c):

(v) the compound (I):

(vi) the compound (p):

(vii) the compound (v):

(viii) the compound (w):

(ix) the compound (x):

(x) the compound (aa)

(xi) the compound (bb)

The compounds of formula (I) and the compounds (a), (b), (c), (l), (p),(v), (w), (x), (aa) and (bb) can be in the E,E-, E,Z- or Z,Z-geometricalisomeric forms.

When n=2, “diradical” is understood to mean a divalent radical so thatthe two units

are bonded to one another via this diradical.

Mention may be made, by way of illustration, of the following compoundsq and r:

In the case where n=2, mention may be made, as example of cyclicdivalent —(CH₂)_(m)— radical formed by R₁ and R₂ with the 2 nitrogenatoms, of that of the compound (hh):

Mention may be made, as linear or branched C₁-C₃ alkyl radicals, forexample, of methyl, ethyl, n-propyl, 1-methylethyl or isopropyl.

Mention may be made, as linear or branched C₁-C₈ alkyl radicals, forexample, of methyl, ethyl, n-propyl, 1-methylethyl, isopropyl, n-butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, n-heptyl or n-octyl.

Mention may be made, as C₅-C₆ cycloalkyl radicals, of cyclopentyl orcyclohexyl.

Mention may be made, among the compounds of formula (I), of those of thefollowing formulae (d), (e), (f), (g), (h), (i), (j), (k), (m), (n),(o), (q), (r), (s), (t), (u), (y), (z), (cc), (ee), (ff), (gg) and (hh)or their E,E-, E,Z- or Z,Z-isomers:

Preference will even more particularly be given, among the merocyaninederivatives in accordance with the present invention, to the followingcompounds or their E,E-, E,Z- or Z,Z-isomers:

The merocyanine derivatives in accordance with the invention, inparticular those of formula (I), can be prepared according to a methoddescribed in U.S. Pat. No. 4,045,229 and U.S. Pat. No. 4,195,999,according to the following scheme (Route 1):

in which the R₁, R₂ and A radicals have the same meanings as in theformula (I).

The merocyanine derivatives in accordance with the invention, inparticular those of formula (I), can be prepared according to a methoddescribed in Patent WO 0020388, according to the following scheme (Route2):

in which the R₁, R₂ and A radicals have the same meanings as in theformula (I).

The merocyanine derivatives in accordance with the invention, inparticular those of formula (I) in which A represents —(C═O)OR₃ and R₃denotes an alkyl having at least 3 carbon atoms, can be obtained bytransesterification according to the scheme below, which route isdescribed in Patent US 2008076940 and can use, inter alia, as catalyst,titanium(IV) isopropoxide (Route 3):

The merocyanine derivatives in accordance with the invention, inparticular those of formula (I) in which R₁ and R₂ denote an alkylhaving at least 3 carbon atoms, can be obtained by transamination,according to the scheme below (Route 4):

Among the merocyanine compounds in accordance with the invention, someare novel.

Mention may be made, among these novel compounds, of those correspondingto the following formula (VI):

in which R₃ and n have the same meanings as in the formula (I), andtheir E,E-, E,Z- or Z,Z-isomeric forms.

Mention may be made, as examples of compounds of formula (VI), of thecompounds (m), (o), (s), (t) and (u), and also their E,E-, E,Z- orZ,Z-isomeric forms.

Mention may also be made, among these novel compounds, of the compounds(e), (f), (i), (j), (l), (p), (r), (v), (w), (x), (aa), (ee), (ff), (gg)and (hh), and also their E,E-, E,Z- or Z,Z-isomeric forms.

The hydrophilic or water-soluble merocyanine screening agent or agentsin accordance with the invention can be present in the compositionsaccording to the invention at a concentration of between 0.1 and 10% byweight, preferably between 0.2 and 5% by weight, with respect to thetotal weight of the composition.

The compositions in accordance with the invention can additionallycomprise other additional organic or inorganic UV screening agents whichare active in the UV-A and/or UV-B regions and which are water-solubleor fat-soluble or else insoluble in the cosmetic solvents commonly used.

Of course, a person skilled in the art will take care to choose theoptional additional screening agent or agents and/or their amounts sothat the advantageous properties intrinsically attached to thecompositions in accordance with the invention are not, or notsubstantially, detrimentally affected by the envisaged addition oradditions, in particular the improvement in the photostability of thedibenzoylmethane derivative.

The additional organic screening agents are chosen in particular fromanthranilics; cinnamic derivatives; salicylic derivatives;benzylidenecamphor derivatives; benzophenone derivatives;β,β-diphenylacrylate derivatives; triazine derivatives;phenylbenzotriazole derivatives; benzalmalonate derivatives, inparticular those cited in U.S. Pat. No. 5,624,663; phenylbenzimidazolederivatives; imidazolines; bis-benzazolyl derivatives, such as describedin Patents EP 669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid(PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole)derivatives, such as described in Applications U.S. Pat. No. 5,237,071,U.S. Pat. No. 5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119;benzoxazole derivatives, such as described in Patent Applications EP 0832 642, EP 1 027 883, EP 1 300 137 and DE 10162844; screening polymersand screening silicones, such as those described in particular inApplication WO 93/04665; dimers derived from α-alkylstyrene, such asthose described in Patent Application DE 19855649; 4,4-diarylbutadienes,such as described in Applications EP 0 967 200, DE 19746654, DE19755649, EP-A-1 008 586, EP 1 133 980 and EP 133 981; merocyaninederivatives other than those of formula (I), (a), (b), (c), (l), (p),(v), (w), (x), (aa) or (bb), such as those described in Applications WO04006878, WO 05058269 and WO 06032741; and their mixtures.

Mention may be made, as examples of organic UV screening agents, ofthose denoted below under their INCI names:

Para-Aminobenzoic Acid Derivatives: PABA, Ethyl PABA, EthylDihydroxypropyl PABA,

Ethylhexyl Dimethyl PABA, sold in particular under the name “Escalol507” by ISP,

Glyceryl PABA,

PEG-25 PABA, sold under the name “Uvinul P25” by BASF,

Salicylic Derivatives:

Homosalate, sold under the name “Eusolex HMS” by Rona/EM Industries,Ethylhexyl Salicylate, sold under the name “Neo Heliopan OS” by Symrise,Dipropyleneglycol Salicylate, sold under the name “Dipsal” by Scher,TEA Salicylate, sold under the name “Neo Heliopan TS” by Symrise,

Cinnamic Derivatives:

Ethylhexyl Methoxycinnamate, sold in particular under the trade name“Parsol MCX” by DSM Nutritional Products,

Isopropyl Methoxycinnamate,

Isoamyl Methoxycinnamate, sold under the trade name “Neo Heliopan E1000” by Symrise,

Cinoxate, DEA Methoxycinnamate, Diisopropyl Methylcinnamate, GlycerylEthylhexanoate Dimethoxycinnamate, β,β-Diphenylacrylate Derivatives:

Octocrylene, sold in particular under the trade name “Uvinul N539” byBASF,Etocrylene, sold in particular under the trade name “Uvinul N35” byBASF,

Benzophenone Derivatives:

Benzophenone-1, sold under the trade name “Uvinul 400” by BASF,Benzophenone-2, sold under the trade name “Uvinul D50” by BASF,Benzophenone-3 or Oxybenzone, sold under the trade name “Uvinul M40” byBASF,Benzophenone-4, sold under the trade name “Uvinul MS40” by BASF,

Benzophenone-5,

Benzophenone-6, sold under the trade name “Helisorb 11” by Norquay,Benzophenone-8, sold under the trade name “Spectra-Sorb UV-24” byAmerican Cyanamid,Benzophenone-9, sold under the trade name “Uvinul DS-49” by BASF,

Benzophenone-12,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, sold under thetrade name “Uvinul A+” or in the form of a mixture with octylmethoxycinnamate under the trade name “Uvinul A+B” by BASF,1,1′-(1,4-Piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone](CAS 919803-06-8),

Benzvlidenecamphor Derivatives:

3-Benzylidene camphor, manufactured under the name “Mexoryl SD” byChimex,4-Methylbenzylidene camphor, sold under the name “Eusolex 6300” byMerck, Benzylidene Camphor Sulfonic Acid, manufactured under the name“Mexoryl SL” by Chimex,Camphor Benzalkonium Methosulfate, manufactured under the name “MexorylSO” by Chimex,Terephthalylidene Dicamphor Sulfonic Acid, manufactured under the name“Mexoryl SX” by Chimex,Polyacrylamidomethyl Benzylidene Camphor, manufactured under the name“Mexoryl SW” by Chimex,

Phenvlbenzimidazole Derivatives:

Phenylbenzimidazole Sulfonic Acid, sold in particular under the tradename “Eusolex 232” by Merck,Disodium Phenyl Dibenzimidazole Tetrasulfonate, sold under the tradename “Neo Heliopan AP” by Symrise,

Phenylbenzotriazole Derivatives:

Drometrizole Trisiloxane, sold under the name “Silatrizole” by RhodiaChimie, Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, sold in thesolid form under the trade name “Mixxim BB/100” by Fairmount Chemical orin the micronized form in aqueous dispersion under the trade name“Tinosorb M” by Ciba Specialty Chemicals,

Triazine Derivatives:

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, sold under the tradename “Tinosorb S” by Ciba-Geigy,Ethylhexyl Triazone, sold in particular under the trade name “UvinulT150” by BASF,Diethylhexyl Butamido Triazone, sold under the trade name “Uvasorb HEB”by Sigma 3V,2,4,6-Tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,2,4,6-Tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine,2,4-Bis(dineopentyl 4′-aminobenzalmalonate)-6-(n-butyl4′-aminobenzoate)-s-triazine,2,4-Bis(n-butyl4′-aminobenzoate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyl)-oxy]disiloxanyl}propyl)amino]-s-triazine,The symmetrical triazine screening agents described in U.S. Pat. No.6,225,467, Application WO 2004/085412 (see compounds 6 and 9) or thedocument “Symmetrical Triazine Derivatives”, IP.COM Journal, IP.COM INC,WEST HENRIETTA, N.Y., US (20 Sep. 2004), in particular the2,4,6-tris(biphenyl)-1,3,5-triazines (especially2,4,6-tris(biphenyl-4-yl)-1,3,5-triazine) and2,4,6-tris(terphenyl)-1,3,5-triazine, which is taken up again in theBeiersdorf applications WO 06/035000, WO 06/034982, WO 06/034991, WO06/035007, WO 2006/034992 and WO 2006/034985.

Anthranilic Derivatives:

Menthyl anthranilate, sold under the trade name “Neo Heliopan MA” bySymrise,

Imidazoline Derivatives: Ethylhexyl DimethoxybenzylideneDioxoimidazoline Propionate, Benzalmalonate Derivatives:

Dineopentyl 4′-methoxybenzalmalonate,Polyorganosiloxane comprising benzalmalonate functional groups, such asPolysilicone-15, sold under the trade name “Parsol SLX” byHoffmann-LaRoche,

4,4-Diarylbutadiene Derivatives:

1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene,

Benzoxazole Derivatives:

2,4-bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,sold under the name of Uvasorb K2A by Sigma 3V,and their mixtures.

The preferred additional organic screening agents are chosen from:

Ethylhexyl Methoxycinnamate, Homosalate, Ethylhexyl Salicylate,Octocrylene, Phenylbenzimidazole Sulfonic Acid, Benzophenone-3,Benzophenone-4, Benzophenone-5,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,1,1′-(1,4-Piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone]

4-Methylbenzylidene Camphor, Terephthalylidene Dicamphor Sulfonic Acid,Disodium Phenyl Dibenzimidazole Tetrasulfonate, Ethylhexyl Triazone,Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Diethylhexyl ButamidoTriazone,

2,4,6-Tris(biphenyl-4-yl)-1,3,5-triazine,2,4,6-Tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine,2,4,6-Tris-(diisobutyl 4′-aminobenzalmalonate)-s-triazine,2,4-Bis(dineopentyl 4′-aminobenzalmalonate)-6-(n-butyl4′-aminobenzoate)-s-triazine,2,4-Bis(n-butyl4′-aminobenzoate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyl)-oxy]disiloxanyl}propyl)amino]-s-triazine,

Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, DrometrizoleTrisiloxane, Polysilicone-15,

Dineopentyl 4′-methoxybenzalmalonate,1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene,2,4-Bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,and their mixtures.

The additional inorganic screening agents are chosen from coated oruncoated metal oxide pigments, such as, for example, pigments formed oftitanium oxide (amorphous or crystalline in the rutile and/or anataseform), iron oxide, zinc oxide, zirconium oxide or cerium oxide, whichare all UV photoprotective agents well known per se.

The pigments may or may not be coated.

The coated pigments are pigments which have been subjected to one ormore surface treatments of chemical, electronic, mechanochemical and/ormechanical nature with compounds such as described, for example, inCosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such asamino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants,lecithins, sodium, potassium, zinc, iron or aluminium salts of fattyacids, metal alkoxides (titanium or aluminium alkoxides), polyethylene,silicones, proteins (collagen, elastin), alkanolamines, silicon oxides,metal oxides or sodium hexametaphosphate.

In a known way, the silicones are organosilicon polymers or oligomerscomprising a linear or cyclic and branched or crosslinked structure, ofvariable molecular weight, obtained by polymerization and/orpolycondensation of suitably functionalized silanes and essentiallycomposed of a repetition of main units in which the silicon atoms areconnected to one another via oxygen atoms (siloxane bond), optionallysubstituted hydrocarbon radicals being connected directly to the saidsilicon atoms via a carbon atom.

The term “silicones” also encompasses the silanes necessary for theirpreparation, in particular alkylsilanes.

The silicones used for the coating of the pigments suitable for thepresent invention are preferably chosen from the group consisting ofalkylsilanes, polydialkylsiloxanes and polyalkylhydrosiloxanes. Morepreferably still, the silicones are chosen from the group consisting ofoctyltrimethylsilane, polydimethylsiloxanes andpolymethylhydrosiloxanes.

Of course, the pigments formed of metal oxides may, before theirtreatment with silicones, have been treated with other surfacing agents,in particular with cerium oxide, alumina, silica, aluminium compounds,silicon compounds or their mixtures.

The coated pigments are, for example, titanium oxides coated:

-   -   with silica, such as the product “Sunveil” from Ikeda and the        product “Eusolex T-AVO” from Merck    -   with silica and with iron oxide, such as the product “Sunveil F”        from Ikeda,    -   with silica and with alumina, such as the products        “Microtitanium Dioxide MT 500 SA” and “Microtitanium Dioxide MT        100 SA” from Tayca, “Tioveil” from Tioxide and “Mirasun TiW 60”        from Rhodia,    -   with alumina, such as the products “Tipaque TTO-55 (B)” and        “Tipaque TTO-55 (A)” from Ishihara and “UVT 14/4” from Kemira,    -   with alumina and with aluminium stearate, such as the product        “Microtitanium Dioxide MT 100 TV”, “MT 100 TX”, “MT 100 Z” or        “MT-01” from Tayca and the products “Solaveil CT-10 W”,        “Solaveil CT 100” and “Solaveil CT 200” from Uniqema,    -   with silica, with alumina and with alginic acid, such as the        product “MT-100 AQ” from Tayca,    -   with alumina and with aluminium laurate, such as the product        “Microtitanium Dioxide MT 100 S” from Tayca,    -   with iron oxide and with iron stearate, such as the product        “Microtitanium Dioxide MT 100 F” from Tayca,    -   with zinc oxide and with zinc stearate, such as the product        “BR351” from Tayca,    -   with silica and with alumina and treated with a silicone, such        as the products “Microtitanium Dioxide MT 600 SAS”,        “Microtitanium Dioxide MT 500 SAS” or “Microtitanium Dioxide MT        100 SAS” from Tayca,    -   with silica, with alumina and with aluminium stearate and        treated with a silicone, such as the product “STT-30-DS” from        Titan Kogyo,    -   with silica and treated with a silicone, such as the product        “UV-Titan X 195” from Kemira or the product SMT-100 WRS from        Tayca,    -   with alumina and treated with a silicone, such as the products        “Tipaque TTO-55 (S)” from Ishihara or “UV Titan M 262” from        Kemira,    -   with triethanolamine, such as the product “STT-65-S” from Titan        Kogyo,    -   with stearic acid, such as the product “Tipaque TTO-55 (C)” from        Ishihara,    -   with sodium hexametaphosphate, such as the product        “Microtitanium Dioxide MT 150 W” from Tayca.

Other titanium oxide pigments treated with a silicone are, for example,TiO₂ treated with octyltrimethylsilane, such as that sold under thetrade name “T 805” by Degussa Silices, TiO₂ treated with apolydimethylsiloxane, such as that sold under the trade name “70250Cardre UF TiO2SI3” by Cardre, or anatase/rutile TiO₂ treated with apolydimethylhydrosiloxane, such as that sold under the trade name“Microtitanium Dioxide USP Grade Hydrophobic” by Color Techniques.

The uncoated titanium oxide pigments are, for example, sold by Taycaunder the trade names “Microtitanium Dioxide MT 500 B” or “MicrotitaniumDioxide MT600 B”, by Degussa under the name “P 25”, by Wacker under thename “Oxyde de titane transparent PW”, by Miyoshi Kasei under the name“UFTR”, by Tomen under the name “ITS” and by Tioxide under the name“Tioveil AQ”.

The uncoated zinc oxide pigments are, for example:

-   -   those sold under the name “Z-cote” by Sunsmart;    -   those sold under the name “Nanox” by Elementis;    -   those sold under the name “Nanogard WCD 2025” by Nanophase        Technologies.

The coated zinc oxide pigments are, for example:

-   -   those sold under the name “Z-cote HP1” by Sunsmart (ZnO coated        with dimethicone);    -   those sold under the name “Oxide zinc CS-5” by Toshibi (ZnO        coated with polymethylhydrosiloxane);    -   those sold under the name “Nanogard Zinc Oxide FN” by Nanophase        Technologies (as a 40% dispersion in Finsolv TN, C₁₂-C₁₅ alkyl        benzoate);    -   those sold under the name “Daitopersion Zn-30” and “Daitopersion        Zn-50” by Daito (dispersions in oxyethylenated        polydimethylsiloxane/cyclo-polymethylsiloxane comprising 30% or        50% of zinc oxides coated with silica and        polymethylhydrosiloxane);    -   those sold under the name “NFD Ultrafine ZnO” by Daikin (ZnO        coated with phosphate of perfluoroalkyl and copolymer based on        perfluoroalkylethyl as a dispersion in cyclopentasiloxane);    -   those sold under the name “SPD-Z1” by Shin-Etsu (ZnO coated with        silicone-grafted acrylic polymer dispersed in        cyclodimethylsiloxane);    -   those sold under the name “Escalol Z100” by ISP (alumina-treated        ZnO dispersed in the ethylhexyl methoxycinnamate/PVP-hexadecene        copolymer/methicone mixture);    -   those sold under the name “Fuji ZnO-SMS-10” by Fuji Pigment (ZnO        coated with silica and polymethylsilsesquioxane);    -   those sold under the name “Nanox Gel TN” by Elementis (ZnO        dispersed at 55% in C₁₂-C₁₅ alkyl benzoate with hydroxystearic        acid polycondensate).

The uncoated cerium oxide pigments are sold, for example, under the name“Colloidal Cerium Oxide” by Rhône-Poulenc.

The uncoated iron oxide pigments are, for example, sold by Arnaud underthe names “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”,“Nanogard FE 45R AQ” or “Nanogard WCD 2006 (FE 45R)”, or by Mitsubishiunder the name “TY-220”.

The coated iron oxide pigments are, for example, sold by Arnaud underthe names “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B556)”, “Nanogard FE 45 BL 345” or “Nanogard FE 45 BL”, or by BASF underthe name “Oxyde de fer transparent”.

Mention may also be made of mixtures of metal oxides, in particular oftitanium dioxide and of cerium dioxide, including the mixture of equalweights of titanium dioxide coated with silica and of cerium dioxidecoated with silica sold by Ikeda under the name “Sunveil A”, and alsothe mixture of titanium dioxide and of zinc dioxide coated with alumina,with silica and with silicone, such as the product “M 261” sold byKemira, or coated with alumina, with silica and with glycerol, such asthe product “M 211” sold by Kemira.

The additional UV screening agents are generally present in thecompositions according to the invention in proportions ranging from 0.01to 20% by weight, with respect to the total weight of the composition,and preferably ranging from 0.1 to 10% by weight, with respect to thetotal weight of the composition.

The compositions in accordance with the present invention canadditionally comprise conventional cosmetic adjuvants chosen inparticular from oils, waxes, organic solvents, ionic or nonionic andhydrophilic or lipophilic thickeners, softening agents, humectants,opacifiers, stabilizing agents, emollients, silicones, antifoamingagents, fragrances, preservatives, anionic, cationic, nonionic,zwitterionic or amphoteric surfactants, active principles, fillers,polymers, propellants, basifying or acidifying agents or any otheringredient commonly used in the cosmetics and/or dermatological field.

Mention may be made, as oils, for example, of mineral oils (liquidparaffin); vegetable oils (sweet almond, macadamia, blackcurrant seed orjojoba oil); synthetic oils, such as perhydrosqualene, fatty alcohols,fatty amides (such as isopropyl lauroyl sarcosinate, sold under the nameof “Eldew SL-205” by Ajinomoto), fatty acids or esters, such as C₁₂-C₁₅alkyl benzoate, sold under the trade name “Finsolv TN” or “Witconol TN”by Witco, 2-ethylphenyl benzoate, such as the commercial product soldunder the name X-Tend 226® by ISP, octyl palmitate, isopropyl lanolate,triglycerides, including those of capric/caprylic acids, dicaprylylcarbonate, sold under the name “Cetiol CC” by Cognis, or oxyethylenatedor oxypropylenated fatty esters and ethers; silicone oils(cyclomethicone, polydimethylsiloxanes or PDMSs); fluorinated oils;polyalkylenes; or trialkyl trimellitates, such as tridecyl trimellitate.

Mention may be made, as wax, for example, of carnauba wax, beeswax,hydrogenated castor oil, polyethylene waxes and polymethylene waxes,such as that sold under the name Cirebelle 303 by Sasol.

Mention may be made, among organic solvents, for example, of loweralcohols and polyols. The latter can be chosen from glycols and glycolethers, such as ethylene glycol, propylene glycol, butylene glycol,dipropylene glycol or diethylene glycol.

Mention may be made, as hydrophilic thickeners, for example, ofcarboxyvinyl polymers, such as the Carbopols (Carbomers) and thePemulens (acrylate/C₁₀-C₃₀ alkyl acrylate copolymer); polyacrylamides,such as, for example, the crosslinked copolymers sold under the namesSepigel 305 (CTFA name: polyacrylamide/C13-14 isoparaffin/Laureth 7) orSimulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltauratecopolymer/isohexadecane/polysorbate 80) by Seppic; optionallycrosslinked and/or neutralized polymers and copolymers of2-acrylamido-2-methylpropanesulphonic acid, such as thepoly(2-acrylamido-2-methylpropanesulphonic acid) sold by Hoechst underthe trade name “Hostacerin AMPS” (CTFA name: ammoniumpolyacryloyldimethyl taurate) or Simulgel 800, sold by Seppic (CTFAname: sodium polyacryloyldimethyl taurate/polysorbate 80/sorbitanoleate); copolymers of 2-acrylamido-2-methylpropanesulphonic acid and ofhydroxyethyl acrylate, such as Simulgel NS and Sepinov EMT 10, sold bySeppic; cellulose derivatives, such as hydroxyethylcellulose;polysaccharides and in particular gums, such as xanthan gum;water-soluble or water-dispersible silicone derivatives, such as acrylicsilicones, silicone polyethers and cationic silicones; and theirmixtures.

Mention may be made, as lipophilic thickeners, for example, of syntheticpolymers, such as the poly(C₁₀-C₃₀ alkyl acrylates) sold under the names“Intelimer IPA 13-1” and “Intelimer IPA 13-6” by Landec, or of modifiedclays, such as hectorite and its derivatives, such as the products soldunder the Bentone names.

Of course, a person skilled in the art will take care to choose theoptional additional compound or compounds mentioned above and/or theiramounts so that the advantageous properties intrinsically attached tothe compositions in accordance with the invention are not, or notsubstantially, detrimentally affected by the envisaged addition oradditions, in particular the improvement in the photostability of thedibenzoylmethane derivative.

The compositions according to the invention can be prepared according totechniques well known to a person skilled in the art. They can beprovided in particular in the form of a simple or complex (O/W, W/O,O/W/O or W/O/W) emulsion, such as a cream, a milk or a cream gel; in theform of an aqueous gel; or in the form of a lotion. They can optionallybe packaged as an aerosol and be provided in the foam or spray form.

Preferably, the compositions according to the invention are provided inthe form of an oil-in-water or water-in-oil emulsion.

The emulsification processes which can be used are of the paddle orpropeller, rotor-stator and HPH type.

It is also possible, by HPH (between 50 and 800 bar), to obtain stabledispersions with drop sizes which may be as low as 100 nm.

The emulsions generally comprise at least one emulsifying surfactantchosen from amphoteric, anionic, cationic or nonionic emulsifyingsurfactants, used alone or as a mixture. The emulsifiers areappropriately chosen according to the emulsion to be obtained (W/O orO/W emulsion).

Mention may be made, as emulsifying surfactants which can be used forthe preparation of the W/O emulsions, for example, of alkyl esters orethers of sorbitan, of glycerol or of sugars; or silicone surfactants,such as dimethicone copolyols, for example the mixture of cyclomethiconeand of dimethicone copolyol sold under the name “DC 5225 C” by DowCorning, and alkyl dimethicone copolyols, such as lauryl methiconecopolyol, sold under the name “Dow Corning 5200 Formulation Aid” by DowCorning, or cetyl dimethicone copolyol, such as the product sold underthe name Abil EM 90R by Goldschmidt and the mixture of cetyl dimethiconecopolyol, of polyglycerol (4 mol) isostearate and of hexyl laurate soldunder the name Abil WE O9 by Goldschmidt. It is also possible to addthereto one or more coemulsifiers which, advantageously, can be chosenfrom the group consisting of polyol alkyl esters.

Mention may in particular be made, as polyol alkyl esters, ofpolyethylene glycol esters, such as PEG-30 dipolyhydroxystearate, suchas the product sold under the name Arlacel P135 by ICI.

Mention may be made, as glycerol and/or sorbitan esters, for example, ofpolyglycerol isostearate, such as the product sold under the name IsolanGI 34 by Goldschmidt; sorbitan isostearate, such as the product soldunder the name Arlacel 987 by ICI; sorbitan glyceryl isostearate, suchas the product sold under the name Arlacel 986 by ICI, and theirmixtures.

Mention may be made, for the O/W emulsions, for example, as emulsifyingsurfactants, of nonionic emulsifiers, such as oxyalkylenated (moreparticularly polyoxyethylenated) esters of fatty acids and of glycerol;oxyalkylenated esters of fatty acids and of sorbitan; oxyalkylenated(oxyethylenated and/or oxypropylenated) esters of fatty acids, such asthe PEG-100 stearate/glyceryl stearate mixture sold, for example, by ICIunder the name Arlacel 165; oxyalkylenated (oxyethylenated and/oroxypropylenated) ethers of fatty alcohols; esters of sugars, such assucrose stearate; or ethers of fatty alcohol and of sugar, in particularalkyl polyglucosides (APGs), such as decyl glucoside and laurylglucoside, sold, for example, by Henkel under the respective namesPlantaren 2000 and Plantaren 1200, cetearyl glucoside, optionally as amixture with cetearyl alcohol, sold, for example, under the nameMontanov 68 by Seppic, under the name Tegocare CG90 by Goldschmidt andunder the name Emulgade KE3302 by Henkel, and arachidyl glucoside, forexample in the form of the mixture of arachidyl and behenyl alcohols andof arachidyl glucoside sold under the name Montanov 202 by Seppic.According to a specific embodiment of the invention, the mixture of thealkyl polyglucoside as defined above with the corresponding fattyalcohol can be in the form of a self-emulsifying composition, forexample as described in the document WO-A-92/06778.

When an emulsion is involved, the aqueous phase of the latter cancomprise a nonionic vesicular dispersion prepared according to knownprocesses (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965),FR 2 315 991 and FR 2 416 008).

The compositions according to the invention have applications in a largenumber of treatments, in particular cosmetic treatments, of the skin,lips and hair, including the scalp, in particular for protecting and/orcaring for the skin, lips and/or hair and/or for making up the skinand/or lips.

Another subject-matter of the present invention is composed of the useof the compositions according to the invention as defined above in themanufacture of products for the cosmetic treatment of the skin, lips,nails, hair, eyelashes, eyebrows and/or scalp, in particular of careproducts, sun protection products and make-up products.

The cosmetic compositions according to the invention can, for example,be used as make-up product.

The cosmetic compositions according to the invention can, for example,be used as care product and/or sun protection product for the faceand/or body with a liquid to semi-liquid consistency, such as milks,relatively smooth creams, cream gels or pastes. They can optionally bepackaged as an aerosol and be provided in the form of a foam or of aspray.

The compositions according to the invention in the form of vaporizablefluid lotions in accordance with the invention are applied to the skinor hair in the form of fine particles by means of pressurizing devices.The devices in accordance with the invention are well known to a personskilled in the art and comprise nonaerosol pumps or “atomizers”, aerosolcontainers comprising a propellant and aerosol pumps using compressedair as propellant. The latter are described in U.S. Pat. No. 4,077,441and U.S. Pat. No. 4,850,517 (forming an integral part of the content ofthe description).

The compositions packaged as an aerosol in accordance with the inventiongenerally comprise conventional propellants, such as, for example,hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane,dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane.They are preferably present in amounts ranging from 15 to 50% by weight,with respect to the total weight of the composition.

The compositions according to the invention can, in addition, alsocomprise additional cosmetic and determatological active principles.

Mention may be made, among active principles, of:

-   -   vitamins (A, C, E, K, PP, and the like) and their derivatives or        precursors, alone or as mixtures;    -   antiaging agents;    -   antioxidants;    -   agents for combating free radicals;    -   antiglycation agents;    -   soothing agents;    -   NO-synthase inhibitors;    -   agents which stimulate the synthesis of dermal or epidermal        macromolecules and/or which prevent their decomposition;    -   agents which stimulate the proliferation of fibroblasts;    -   agents which stimulate the proliferation of keratinocytes;    -   dermo-decontracting agents;    -   tightening agents;    -   matifying agents;    -   keratolytic agents;    -   desquamating agents;    -   moisturizing agents, such as, for example, polyols, such as        glycerol, butylene glycol or propylene glycol;    -   agents which act on the energy metabolism of the cells;    -   insect repellents;    -   substance P or substance CRGP antagonists;    -   agents for combating hair loss and/or for the regrowth of the        hair;    -   antiwrinkle agents;    -   agents which modulate the pigmentation of the skin or hair;    -   astringent agents;    -   sebum-regulating agents or antiseborrhoeics.

Of course, a person skilled in the art will take care to choose theoptional additional compound or compounds mentioned above and/or theiramounts so that the advantageous properties intrinsically attached tothe compositions in accordance with the invention are not, or notsubstantially, detrimentally affected by the envisaged addition oradditions.

A person skilled in the art will choose the said active principle orprinciples according to the effect desired on the skin, hair, eyelashes,eyebrows or nails.

In addition, the composition can comprise at least one ingredient, suchas fillers having a soft focus effect or agents which promote thenatural colouring of the skin, intended to supplement the biologicaleffect of these active principles or to contribute an immediate visualantiaging effect.

Other Additional Ingredients

In addition, the composition can comprise at least one additionalingredient intended to contribute an immediate visual effect. Mentionmay in particular be made of agents which promote the naturally pinkcolouring of the skin.

Mention may be made, as agents which promote the naturally pinkcolouring of the skin, for example, of self-tanning agents, that is tosay an agent which, applied to the skin, in particular to the face,makes it possible to obtain a tanning effect with an appearance more orless similar to that which can result from prolonged exposure to the sun(natural tanning) or under a UV lamp.

Mention may in particular be made, as examples of self-tanning agents,of:

dihydroxyacetone (DHA),erythrulose, andthe combination of a catalytic system formed of:manganese and/or zinc salts and oxides, andalkali metal and/or alkaline earth metal hydrogencarbonates.

The self-tanning agents are generally chosen from mono- or polycarbonylcompounds, such as, for example, isatin, alloxan, ninhydrin,glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose,pyrazoline-4,5-dione derivatives, such as described in PatentApplications FR 2 466 492 and WO 97/35842, dihydroxyacetone (DHA) or4,4-dihydroxypyrazolin-5-one derivatives, such as described in PatentApplication EP 903 342. Use will preferably be made of DHA.

The DHA can be used in the free and/or encapsulated form, for exampleencapsulated in lipid vesicules, such as liposomes, described inparticular in Application WO 97/25970.

Generally, the self-tanning agent is present in an amount ranging from0.01 to 20% by weight and preferably in an amount of between 0.1 and 10%of the total weight of the composition.

Use may also be made of other dyes which make it possible to modify thecolour produced by the self-tanning agent.

These dyes can be chosen from synthetic or natural direct dyes.

These dyes can be chosen, for example, from red or orange dyes of thefluoran type, such as those described in Patent Application FR 2 840806. Mention may be made, for example, of the following dyes:

-   -   tetrabromofluorescein or eosin, known under the CTFA name: CI        45380 or Red 21;    -   phloxine B, known under the CTFA name: CI 45410 or Red 27;    -   diiodofluorescein, known under the CTFA name: CI 45425 or Orange        10;    -   dibromofluorescein, known under the CTFA name: CI 45370 or        Orange 5;    -   the sodium salt of tetrabromofluorescein, known under the CTFA        name: CI 45380 (Na salt) or Red 22;    -   the sodium salt of phloxine B, known under the CTFA name: CI        45410 (Na salt) or Red 28;    -   the sodium salt of diiodofluorescein, known under the CTFA name:        CI 45425 (Na salt) or Orange 11;    -   erythrosine, known under the CTFA name: CI 45430 or Acid Red 51;    -   phloxine, known under the CTFA name: CI 45405 or Acid Red 98.

These dyes can also be chosen from anthraquinones, caramel, carmine,carbon black, azulene blues, methoxsalen, trioxsalen, guaiazulene,chamazulene, rose bengal, eosin 10B, cyanosine or daphinine.

These dyes can also be chosen from indole derivatives, such asmonohydroxy-indoles, such as described in Patent FR 2 651 126 (i.e.: 4-,5-, 6- or 7-hydroxyindole), or dihydroxyindoles, such as described inPatent EP-B-0 425 324 (i.e.: 5,6-dihydroxyindole,2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole or2,3-dimethyl-5,6-dihydroxyindole).

The examples which follow serve to illustrate the invention, but withouthaving any limiting character. In these examples, the amounts of theingredients of the compositions are given as % by weight, with respectto the total weight of the composition.

SYNTHETIC EXAMPLES Example 1 Preparation of butyl(2E,4E)-5-[bis(2-hydroxyethyl)amino]-2-cyanopenta-2,4-dienoate

First Stage: Preparation of butyl(2E,4E)-5-[acetyl(phenyl)amino]-2-cyanopenta-2,4-dienoate

3-Anilinoacrolein-aniline (3 g, 13.5×10⁻³ mol) and n-butyl cyanoacetate(1.9 ml, 13.5×10⁻³ mol) are heated in 6 ml of acetic anhydride for 1hour 30 minutes at 85-90° C. while bubbling with nitrogen. Aftercooling, 10 ml of methanol are added and precipitation is allowed totake place. The solid obtained is filtered off and rinsed with methanol.Drying is carried out. 3.14 g (yield: 74%) of a yellow powder of butyl(2E,4E)-5-[acetyl(phenyl)amino]-2-cyanopenta-2,4-dienoate are recovered,which powder is used as is in the following stage.

Second Stage: Preparation of the Compound of Example 1

A solution of the preceding product (3.1 g, 0.01 mol) and ofdiethanolamine (1.04 g, 0.01 mol) in 6 ml of acetonitrile is brought toreflux for 4 hours. After cooling, the mixture is evaporated to drynessunder vacuum. The orange-coloured residue is chromatographed on a silicacolumn (gradient of eluents: CH₂Cl₂/MeOH 100:0 to 90:10). 1.32 g (yield:47%) of the pure fractions of the derivative of Example 1 are thusobtained in the form of a pale yellow powder:

M.P.: 50-52° C.

UV (Ethanol): λ_(max)=382 nm, E1%=2270.

Example 2 Preparation ofhexyl(2E,4E)-5-[bis(2-hydroxyethyl)amino]-2-cyanopenta-2,4-dienoate

First Stage: Preparation of hexyl(2E,4E)-5-[acetyl(phenyl)amino]-2-cyanopenta-2,4-dienoate

3-Anilinoacrolein-aniline (2 g, 9×10⁻³ mol) and n-hexyl cyanoacetate(1.52 g, 9×10⁻³ mol) are heated in 5 ml of acetic anhydride at 105° C.for 3 hours while bubbling with nitrogen. After cooling, 10 ml ofmethanol are added and precipitation is allowed to take place. The solidobtained is filtered off and rinsed with methanol. Drying is carriedout. 1.2 g of a yellow powder (yield: 32%) of hexyl(2E,4E)-5-[acetyl(phenyl)amino]-2-cyanopenta-2,4-dienoate are recovered,which powder is used as is in the following stage.

Second Stage: Preparation of the Compound of Example 2

A solution of the preceding product (1 g, 2.94×10⁻³ mol) and ofdiethanolamine (0.31 g, 2.94×10⁻³ mol) in 5 ml of acetonitrile isbrought to reflux for 1 hour 15 minutes. After cooling, the mixture isevaporated to dryness under vacuum.

The brown residue obtained is chromatographed on a silica column(gradient of eluents: CH₂Cl₂/MeOH 100:0 to 98:2). 0.51 g (yield: 55%) ofthe pure fractions of the derivative of Example 2 is thus obtained inthe form of a pale yellow powder:

M.P.: 76-78° C.

UV (Ethanol): λ_(max)=381 nm, E1%=1846.

Example 3 Preparation of n-octyl(2E,4E)-5-[bis(2-hydroxyethyl)amino]-2-cyanopenta-2,4-dienoate

First Stage: Preparation of n-octyl(2E,4E)-5-[acetyl(phenyl)amino]-2-cyanopenta-2,4-dienoate

3-Anilinoacrolein-aniline (27.7 g, 0.125 mol) and n-octyl cyanoacetate(26.3 ml, 0.125 mol) are heated in 70 ml of acetic anhydride at 115° C.for 2 hours while bubbling with nitrogen. After cooling, 80 ml ofmethanol are added and precipitation is allowed to take place. The solidobtained is filtered off and rinsed with methanol. Drying is carriedout. 36.4 g of a yellow powder (yield: 79%) of butyl(2E,4E)-5-[acetyl(phenyl)amino]-2-cyanopenta-2,4-dienoate are recovered,which powder is used as is in the following stage.

Second Stage: Preparation of the Compound of Example 3

A solution of the preceding product (36.2 g, 0.00982 mol) and ofdiethanolamine (10.33 g, 0.00982 mol) in 75 ml of acetonitrile isbrought to reflux for 1 hour 30 minutes. After cooling in an ice bath,the product precipitates. The solid is filtered off and rinsed with apiston of cold acetonitrile. The solid is recrystallized twice fromethyl ether. 18.9 g (yield: 57%) of the derivative of Example 3 are thusobtained in the form of a pale yellow powder:

M.P.: 81-84° C.

UV (Ethanol): λ_(max)=382 nm, E1%=1725.

Example 4 Preparation of n-octyl(2E,4E)-2-cyano-5-(diethylamino)penta-2,4-dienoate

Diethylamine (14.5 ml, 0.14 mol) and propargyl alcohol (6.81 ml, 0.117mol) are dissolved in 100 ml of toluene. 34.5 g of manganese dioxide(activated, <5 μm; 3.4 equiv.) are added portionwise while controllingthe strong exotherm (temperature <50° C.) and the mixture is leftstirring at 52° C. for 20 hours. The reaction mixture is filtered. Theyellow filtrate is poured into a reactor surmounted by a Dean and Starkapparatus. n-Octyl cyanoacetate (23 g, 0.117 mol) and catalyst (0.1equiv., 0.667 ml of acetic acid and 1.2 ml of N,N-diethylamine) areadded with stirring and the reaction mixture is brought to reflux. It isleft at reflux for 5 hours 30 minutes. After cooling, dichloromethane isadded and washing is carried out once with a saturated sodiumbicarbonate solution and then once with water. The organic phase isdried and then concentrated under vacuum. The brown red oil obtained ischromatographed on a silica column (gradient of eluents: heptane/AcOEt90:10 to 80:20). 26 g (yield: 72%) of the pure fractions of thederivative of Example 4 are thus obtained in the form of anorange-coloured gum which crystallizes; recrystallization from heptanegave the derivative of Example 4 in the form of a yellow powder:

M.P.: 48-49° C.

UV (Ethanol): λ_(max)=381 nm, E1%=2274.

Example 5 Preparation of 2-ethylhexyl(2E,4E)-2-cyano-5-(diethylamino)-penta-2,4-dienoate

Diethylamine (30 g, 0.41 mol) and propargyl alcohol (18.4 g, 0.328 mol)are dissolved in 250 ml of toluene. 72.6 g of manganese dioxide(activated, <5 μm; 2.5 equiv.) are added portionwise while controllingthe strong exotherm (temperature <50° C.) and the mixture is leftstirring at 90° C. for 5 hours. The reaction mixture is filtered. Theyellow filtrate is poured into a reactor surmounted by a Dean and Starkapparatus. 2-Ethylhexyl cyanoacetate (61.5 g, 0.312 mol) and catalyst(0.1 equiv., 1.77 ml of acetic acid and 3.2 ml of N,N-diethylamine) areadded with stirring and the reaction mixture is brought to reflux. It isleft at reflux for 5 hours 30 minutes. After cooling, 500 ml ofdichloromethane are added and washing is carried out once with asaturated sodium bicarbonate solution and then twice with water. Theorganic phase is dried and then purified on a silica bed. The firstfractions are recovered and concentrated under vacuum. 21.9 g (yield:23%) of the pure fractions of the derivative of Example 5 are thusobtained in the form of an orange-coloured gum which crystallizes;recrystallization from heptane gave the derivative of Example 5 in theform of a yellow powder:

M.P.: 32-37° C.

UV (Ethanol): λ_(max)=381 nm, E1%=2240.

Example 6 Preparation of methyl(2E,4E)-2-cyano-5-(dimethylamino)-penta-2,4-dienoate

N,N-Dimethylacrolein (80.52 ml, 0.772 mol) is dissolved in 460 ml oftoluene while bubbling with nitrogen and the catalyst, a mixture ofacetic acid (8.85 ml, 0.2 equiv.) and of n-octylamine (3.83 ml, 0.03equiv.), is added. The mixture is heated to reflux and methylcyanoacetate (69.48 ml, 0.787 mol) is added dropwise over 45 minutes.The water is removed by azeotropic distillation. The reaction is haltedafter 2 hours 30 minutes. The solvent is evaporated under vacuum. 152 gof a light brown powder are obtained, which powder is crystallized fromisopropanol to give 118.5 g (yield: 85%) of the derivative of Example 6in the form of a pale yellow powder:

M.P.: 158-159° C.

UV (Ethanol): λ_(max)=378 nm, E1%=3564.

Example 7 Preparation of octyl(2E,4E)-2-cyano-5-(dimethylamino)penta-2,4-dienoate

N,N-Dimethylacrolein (37.4 ml, 0.374 mol) is dissolved in 500 ml oftoluene while bubbling with nitrogen and the catalyst, a mixture ofacetic acid (4.1 ml, 0.2 equiv.) and of n-octylamine (1.8 ml, 0.03equiv.), is added. The mixture is heated to reflux and n-octylcyanoacetate (76 ml, 0.359 mol) is added dropwise over 25 minutes. Thewater is removed by azeotropic distillation. The reaction is haltedafter 2 hours. The solvent is evaporated under vacuum. 123 g of anorangey brown solid are obtained, which solid is recrystallized fromisopropanol to give 118.5 g (yield: 85%) of the derivative of Example 7in the form of pale yellow needles:

M.P.: 80-81° C.

UV (Ethanol): λ_(max)=380 nm, E1%=2186.

Example 8 Preparation of 2,3-dihydroxypropyl(2E,4E)-2-cyano-5-(dimethylamino)penta-2,4-dienoate)

First Stage: Preparation of (2,2-dimethyl-1,3-dioxolan-4-yl)methylcyanoacetate

A mixture of methyl cyanoacetate (1.3 ml, 15×10⁻³ mol), of solketal(1.25 ml, 10×10⁻³ mol) and of DMAP (2.7 mg, 0.03 equiv.) is heated atreflux with stirring for 30 hours in a reactor rendered inert withnitrogen. After cooling, the solvent is evaporated under vacuum and thebrown oil obtained is chromatographed on a silica column (gradient ofeluents: heptane/EtOAc from 90:10 to 80:20). 423 mg (yield: 23%) of thepure fractions of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetateare thus obtained in the form of a yellow oil used as is in thefollowing stage.

Second Stage: Preparation of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl(2E,4E)-2-cyano-5-(dimethylamino)penta-2,4-dienoate

The preceding product (50 mg, 0.254×10⁻³ mol) and the catalysts,n-octylamine (1.3 μl, 0.03 equiv.) and acetic acid (3 μl, 0.2 equiv.),in 0.8 ml of toluene are brought to reflux in a reactor rendered inertwith nitrogen. N,N-Dimethylacrolein (26 μl, 0.25×10⁻³ mol), dissolved in0.8 ml of toluene, is added dropwise to the reaction mixture. Reflux ismaintained for 36 hours while adding the same amounts of catalyst every8 hours. After cooling, the solvent is evaporated under vacuum and thebrown paste obtained is crystallized from 2 ml of isopropanol. 68 mg(yield: 97%) of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl(2E,4E)-2-cyano-5-(dimethylamino)penta-2,4-dienoate are thus obtained inthe form of a beige powder used as is in the following stage:

UV (Ethanol): λ_(max)=379 nm, E1%=1974.

Third Stage: Preparation of the Compound of Example 8

The preceding product (60 mg, 0.21×10⁻³ mol) is dissolved in an MeOH/THF1:1 mixture in a reactor rendered inert with nitrogen. Dowex H+ (1 g) isadded thereto and the mixture is left stirring for 24 hours. Afterfiltering off the Dowex and evaporating the solvents, the residue ischromatographed on a silica column (eluent: CH₂Cl₂/MeOH 95:5). 22 mg(yield: 43%) of the pure fractions of the derivative of Example 8 arethus obtained in the form of a viscous orange-coloured oil:

UV (Ethanol): λ_(max)=375 nm, E1%=1485.

Example 9 Preparation of n-octyl(2E,4E)-2-cyano-5-(piperidin-1-yl)penta-2,4-dienoate

The derivative of Example 4 (15.5 g, 0.051 mol) is heated at 60° C. for2 hours with 100 ml of piperidine while bubbling with nitrogen. Heatingis continued at 80° C. for 6 hours. After cooling the reaction mixture,it is poured into 2 litres of water. The precipitate obtained isfiltered off and is washed with 3 pistons of water. After drying, 12.57g (yield: 75%) of the derivative of Example 9 are obtained in the formof a pale yellow powder:

M.P.: 87-89° C.

UV (Ethanol): λ_(max)=382 nm, E1%=2270.

Formulation Examples

The following oil/water emulsions are prepared; the amounts areexpressed as percentages by weight, with respect to the total weight ofeach composition.

Formulation Formulation Composition 1 2 Polydimethylsiloxane 0.5 0.5Preservatives 1 1 Stearic acid 1.5 1.5 Glyceryl monostearate/PEG (100 11 EO) stearate mixture Mixture of cetearyl glucoside and of 2 2 cetyland stearyl alcohols Cetyl alcohol 0.5 0.54-(tert-Butyl)-4′-methoxydibenzoyl- 2 2 methane C₁₂/C₁₅ Alkyl benzoate10 10 Derivative of Example 4: compound (e) 1 2 Deionized water q.s. for100 q.s. for 100 Complexing agent 0.1 0.1 Glycerol 5 5 Xanthan gum 0.20.2 Monocetyl phosphate 1 1 Isohexadecane 1 1 Acrylic acid/stearylmethacrylate copolymer 0.2 0.2 Triethanolamine q.s. for pH q.s. for pH

Procedure:

The aqueous phase (Phase B) comprising all of its ingredients is heatedto 80° C. in a water bath. The fatty phase (Phase A) comprising all ofits ingredients is heated to 80° C. in a water bath. A is emulsified inB with stirring of rotor-stator type (device from Moritz). Phase C isincorporated and the mixture is allowed to return to ambient temperaturewith moderate stirring. The triethanolamine is introduced so as toadjust the pH to the value desired at the end of manufacture.

Tests of Photostability of the Dibenzoylmethane Screening Agent

The following emulsions are prepared:

Formulations Ai (invention):

Cetearyl glucoside/cetearyl alcohol mixture 7.5 g (Montanov 68) C₁₂/C₁₅Alkyl benzoate (Witconol TN, Witco) 20 g Compound of the invention(compound (e), (f) or (g)) 2 g 4-(tert-Butyl)-4′-methoxydibenzoylmethane(avobenzone) 1 g Glycerol 5 g Preservatives q.s. Demineralized waterq.s. for 100 gFormulations Bi (outside the invention):

Cetearyl glucoside/cetearyl alcohol mixture 7.5 g (Montanov 68) C₁₂/C₁₅Alkyl benzoate (Witconol TN, Witco) 20 g Comparative compound (compoundb₁, b₂, b₃ or b₄ outside the invention) 2 g4-(tert-Butyl)-4′-methoxydibenzoylmethane 1 g (avobenzone) Glycerol 5 gPreservatives q.s. Demineralized water q.s. for 100 g

Approximately 20 mg of the preceding emulsion are spread over 10 cm² ofthe surface of a ground silica disc; the exact amount of the depositedlayer is determined by weighing.

The films of the solutions are irradiated for 1 hour using an Orielsolar simulator (UV-A flux=14.4 mW/cm²; UV-B flux=0.43 mW/cm²) with adose of 12 J/cm² and are then extracted with 10 ml of ethanol comprising10% of isopropanol and subjected to ultrasound for 5 min. The productsare quantified by HPLC of the extracts.

The degrees of loss are determined by comparison of the amounts ofproduct present in the irradiated samples and in the non-irradiatedcontrols prepared simultaneously and treated in the same way (means over3 samples).

Photostability Results Comparative Example b₁ Family of the CyclicDicyano Compounds

Comparative Example b₂ Family of the Cyclic Dicyano Compounds

Comparative Example b₃ Family of the Cyclic Cyanoacetates

Comparative Example b₄ Family of the Phenyl Sulphone Acetates

TABLE OF THE PHOTOSTABILITY RESULTS % of % of disappearancedisappearance of the of the merocyanine avobenzone compound Compositiontested (mean loss) (mean loss) Formulation A₁ (invention): 1.6% 1.1% 1%avobenzone + 2% compound (e) Formulation A₂ (invention): 7.0% 7.0% 1%avobenzone + 2% compound (f) Formulation A₃ (invention): 6.8% 3.5% 1%avobenzone + 2% compound (g) Formulation B₁ (outside the invention)27.5% 21.6% 1% avobenzone + 2% compound (b₁) Formulation B₂ (outside theinvention) 17.3% 20.0% 1% avobenzone + 2% compound (b₂) Formulation B₃(outside the invention) 18.1% 21.7% 1% avobenzone + 2% compound (b₃)Formulation B₄ (outside the invention) 14.4% 15.4% 1% avobenzone + 2%compound (b₄)

The compounds of the invention (e), (f) and (g) respectively present inthe formulations A₁ to A₃ photostabilize the avobenzone better than thecomparative compounds b₁, b₂, b₃ and b₄ present in the formulations B₁to B₄ and do this in a significant way

The compounds of the invention (e), (f) and (g) respectively present inthe formulations A₁ to A₃ do not or virtually do not photodecompose inthe presence of avobenzone, in contrast to the comparative compounds b₁,b₂, b₃ and b₄.

1. A compound corresponding to the following formula (VI):

wherein R₃ denotes a linear or branched C₁-C₈ alkyl radical, and n is 1or 2, and their E,E-, E,Z- or Z,Z-isomeric forms.
 2. The compoundaccording to claim 1, chosen from those of the following formulae andtheir E,E-, E,Z- or Z,Z-isomeric forms:


3. A compound chosen from the following compounds and their E,E-, E,Z-or Z,Z-isomeric forms: